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Abstract:

The invention relates to a method for producing
3,7-diaza-bicyclo[3.3.1]nonane metal complexes, wherein the ligand, a
3,7-diaza-bicyclo[3.3.1] nonane compound, is reacted with an aqueous
metal(II)salt solution in one step. According to the invention, the
reaction stage is carried out with water as solvent.

Claims:

1. A method for producing 3,7-diazabicyclo[3.3.1]nonane metal complexes
of the formula (2) [MaLkZ.sub.n]Ym (2) wherein M is
selected from the group consisting of the following metals:
Mn(II)-(III)-(IV), Cu(I)-(II)-(III), Fe(II)-(III)-(IV)-(V) and
Co(I)-(II)-(III); L is a ligand of the formula (1) or its protonated or
deprotonated form, wherein R is hydrogen, hydroxyl, or
C1-C4-alkyl; R1 is C1-C4-alkyl,
C6-C10-aryl, pyridinyl-C1-C4-alkyl, or
(CH2).sub.n1N(CH3)2; R2 is C1-C4-alkyl, or
C6-C10-aryl; R3 is C1-C4-alkyl, X is C=O or
C(OH)2, ##STR00003## Z is a coordinating compound selected from
mono-, bi- or tri-charged anions or neutral molecules which can
coordinate to a metal in mono-, bi- or tri-dentate form, such as e.g.:
OH--, NO.sub.3.sup.--, NO, S2--, RS--, PO.sub.4.sup.3--,
H2O, CO.sub.3.sup.2--, ROH, Cl--, Br--,
CN--,ClO.sub.4.sup.--, RCOO--, SO.sub.4.sup.2--; Y is an anion
balancing the charge of he complex; a is an integer from 1 to 10, k is an
integer from 1 to 10; n is an integer from 1 to 10, m is an integer from
1 to 20, wherein the method comprises dissolving or suspending the ligand
L in water and complexing it with a metal salt

2. The method as claimed in claim 1, wherein the metal salt is Fe(II)
chloride.

4. The method as claimed in claim 1, wherein the metal salt for
complexing the ligand L is a solid or in the form of an aqueous metal
salt solution.

5. The method as claimed in claim 1, wherein the method is carried out at
room temperature.

6. The method as claimed in claim , wherein a is an integer from 1 to 4.

7. The method as claimed in claim 1, wherein n is an integer from 1 to 4.

8. The method as claimed in claim 1, wherein m is an integer from 1 to 8.

Description:

[0001] 3,7-Diazabicyclo[3.3.1]nonane ligands of the formula (1) are
interesting compounds for various applications. Inter alia, their
transition metal complexes are very effective bleach and oxidation
catalysts.

##STR00001##

[0002] Their use as bleach catalyst in detergents and cleaners is claimed
inter alia in WO 02/48301, US 2003/0 162 681 and WO 03/104 234.

[0003] The production of these iron complexes is described inter alia in
Inorg. Chimica Acta, 337 (2002) 407-419 on a laboratory scale. Patent
applications such as EP 0765381, EP 0909809 and WO 02/48301 likewise show
the synthesis of these metal complexes.

[0004] These known syntheses take place by reacting the particular ligand
with a metal salt in an organic solvent such as acetonitrile. The process
is carried out under argon or nitrogen and anhydrous conditions. The
yields here are only moderate and lie between 40 and 70%. For isolating
the end product, the described synthesis method requires high solvent
additions for the purification, such as e.g. methanol, acetic ester,
acetone or dichloromethane. The choice of solvents and the strictly
anhydrous conditions (anhydrous solvents, argon or nitrogen blanketing of
the reaction) lead to problems and an increase in cost in the case of
reaction on an industrial scale.

[0005] The object of the present invention is to find an improved and
simplified method for producing these metal complexes. Surprisingly, it
has now been found that the reaction of ligand and metal salt can be
carried out in aqueous solution or suspension, giving the desired metal
complexes in high yields and purities.

[0006] The invention therefore provides a method for producing
3,7-diazabicyclo[3.3.1]nonane metal complexes of the formula (2)

[MaLkZ.sub.n]Ym (2)

in which M represents the following metals: Mn(II)-(III)-(IV),
Cu(I)-(II)-(III), Fe(II)-(III)-(IV)-(V) and Co(I)-(II)-(II);

[0007] L is a ligand of the formula (1) or its protonated or deprotonated
form, where R can be hydrogen, hydroxyl, C1-C4-alkyl; R1
can be C1-C4-alkyl, C6-C10-aryl,
pyridinyl-C1-C4-alkyl, (CH2).sub.n1N(CH3)2 (n1
is preferably 1-10); R2 can be C1-C4-alkyl,
C6-C10-aryl; R3 can be C1-C4-alkyl, X can be C=O
or C(OH)2,

[0015] The method according to the invention very generally consists in
dissolving or suspending, preferably suspending, the ligand in water, and
complexing it with a metal salt. The metal salt contains a metal M as
metal and an anion Y as anion. The metal salt used is preferably a
metal(II) salt and particularly preferably Fe(II) chloride. Particular
preference is given to producing the compound iron (1+), chloro[dimethyl
9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-KN)-7-[(2-pyridinyl-KN)methyl]--
3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate-KN3, Kn7]-, chloride
(1:1).

[0016] For complexing the ligand L, the metal salt is preferably added to
the aqueous solution or suspension of the ligand L either in the form of
a solid or in the form of an aqueous metal salt solution.

[0017] The method according to the invention is preferably carried out at
room temperature.

[0018] The synthesis preferably takes place by suspending the ligand (1)
in water within 30 to 60 minutes with vigorous mixing and, with stirring,
admixing it with an equimolar amount of aqueous iron(II) salt solution
with a concentration of preferably 30% by weight of Fe(II) salt. The
weight ratio of water to ligand during the dissolution process here is
approximately 4:1 to 1:1, preferably 1.6:1. The molar ratio of ligand to
iron(II) salt is ca. 0.9:1.2 to 1.2:0.9, preferably 1:1.05. After being
stirred for 3 to 5 hours at room temperature, the solution is isolated by
spray granulation or filtration and drying. The yield is ca. 98% with a
purity of 95-98%.

[0019] The method according to the invention takes place in water. With
the method according to the invention, a higher yield is achieved
compared to the methods according to the prior art. Moreover, by
dispensing with organic solvents, the method according to the invention
operates in a considerably more cost-effective manner.

[0020] The examples below serve to illustrate the invention in more detail
without limiting it thereto.

EXAMPLES

Example 1

[0021] 33.6 kg (2000 mol) of water and 20.6 kg (40 mol) of
2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]-
nonan-9-one 1,5-dimethyldicarboxylate (N2Py3o) were charged to a reaction
vessel and stirred to give a homogeneous solution within 30 minutes. The
reaction vessel was closed and filled with nitrogen. After rendering it
inert with nitrogen, 17 kg (40.6 mol) of aqueous iron(II) chloride
solution (30.2% strength) were added over the course of 30 minutes and
the dropping funnel was rinsed with 5 kg of water. The reaction solution
was stirred at room temperature for five hours and then dried, preferably
by means of spray-drying methods. In this way, the compound with the name
iron (1+), chloro[dimethyl
9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-KN)-7-[(2-pyridinyl-KN)methyl]--
3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate-KN3, Kn7]-, chloride (1:1)
was obtained.

[0022] The product was obtained as a yellow powder in a purity of >95%
(HPLC) and a yield of 28.2 kg (98%).

Example 2

[0023] 64.45 g (0.125 mol) of the same 3,7-diazabicyclo[3.3.1]nonane
compound as in example 1 were pulverized and suspended in this form in
107.5 g (5.97 mol) of water. 52.28 g of a 30.2% strength iron(II)
chloride solution were then added and the reaction mixture was stirred
for three hours at room temperature. The fine suspension of the product
was then converted to a pulverulent yellow end product by filtration and
drying in a vacuum drying cabinet. In this way, the same product as in
example 1 was obtained in a yield of 81 g (98%) with a purity of >95%
(HPLC).

Patent applications by Barbara Duecker, Mainz DE

Patent applications by Michael Wessling, Kandern DE

Patent applications by CLARIANT FINANCE (BVI) LIMITED

Patent applications in class Polycyclo ring system having the six-membered hetero ring as one of the cyclos

Patent applications in all subclasses Polycyclo ring system having the six-membered hetero ring as one of the cyclos